US9624609B2 - Composite materials - Google Patents

Composite materials Download PDF

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Publication number
US9624609B2
US9624609B2 US13/985,276 US201113985276A US9624609B2 US 9624609 B2 US9624609 B2 US 9624609B2 US 201113985276 A US201113985276 A US 201113985276A US 9624609 B2 US9624609 B2 US 9624609B2
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substrate
fibers
matrix
expanding agent
resin
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US20140220841A1 (en
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Nicolas Rumeau
Aurélie Buisson
Pascal Trouillot
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Roxel France SA
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Roxel France SA
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/04—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres having existing or potential cohesive properties, e.g. natural fibres, prestretched or fibrillated artificial fibres
    • D04H1/08—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres having existing or potential cohesive properties, e.g. natural fibres, prestretched or fibrillated artificial fibres and hardened by felting; Felts or felted products
    • D04H1/10—Felts made from mixtures of fibres
    • D04H1/14—Felts made from mixtures of fibres and incorporating inorganic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/044—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • C08J5/048—Macromolecular compound to be reinforced also in fibrous form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/247—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using fibres of at least two types
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085—Use of fibrous compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/024—Preparation or use of a blowing agent concentrate, i.e. masterbatch in a foamable composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2525—Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2959—Coating or impregnation contains aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2975—Coated or impregnated ceramic fiber fabric

Definitions

  • the present invention relates to the field of composite materials based on fibrous materials and resins. It relates more particularly to the field of composite materials made from natural fibrous materials and aqueous resins.
  • composite materials are commonly used for more or less specialized applications. These composite materials are generally manufactured, in a known manner, starting from a woven or nonwoven, organic or inorganic absorbent material, impregnated with a thermosetting resin.
  • Application EP 0041054 notably describes the formation of such materials.
  • Certain composite materials are constituted in particular of glass fibers, mineral fibers, cellulose or polyester fibers, impregnated with thermosetting resins based on urea-formaldehyde, phenol-formaldehyde, resorcinol-formaldehyde or melamine-formaldehyde combinations.
  • preparation of these materials comprises impregnating the fibers of absorbent material with a solution of resin, a phenol-formaldehyde resin for example, in which microspheres consisting of a polymer material, of the vinylidene chloride/acrylonitrile type, containing an expanding agent of the isobutane type for example, are dispersed.
  • resin a phenol-formaldehyde resin for example, in which microspheres consisting of a polymer material, of the vinylidene chloride/acrylonitrile type, containing an expanding agent of the isobutane type for example, are dispersed.
  • EP 01 02 335 notably describes a method for producing a composite material using cellulose fibers, said method comprising mixing microspheres with a suspension of cellulose fibers. After dewatering, the fibrous network is calendered and heated to 120° C. to initiate expansion. The expanded material is impregnated with an aqueous solution of phenolic resin, then dried by microwave and then the resin is crosslinked.
  • the method described in this application offers the advantage that the composite material can be produced in two steps, which can, to a certain extent, be spread over time. Conversely, it requires two baking phases, the first for causing the microspheres to react, which act as expanding agent and initiate expansion of the material, and the second for crosslinking the resin and imparting rigidity to the material. Therefore there is some complexity in application of this method.
  • the invention relates to a composite material consisting of:
  • the proportions by weight of substrate and of thermosetting matrix used are defined so as to obtain an impregnated substrate having the following proportions by weight after drying:
  • the proportion by weight of expanding agent in the aqueous mixture is between 10% and 15%.
  • the substrate is a felt of basalt fibers.
  • the basalt constituting the fibers forming the substrate contains a proportion of olivine at least equal to 15 wt %.
  • the resin constituting the matrix is a phenol-formaldehyde resin.
  • the resin constituting the matrix is obtained from a bio-source.
  • the expanding agent is formed from microspheres of hydrocarbons coated with a polymer film.
  • the hydrocarbon of the expanding agent is isobutane.
  • the expanding agent is a yeast mixed in the water-based resin.
  • the material according to the invention comprises a substrate of fiber and a thermosetting matrix (aqueous base) in the following proportions by weight:
  • the material according to the invention comprises a substrate of fiber and a thermosetting matrix (aqueous base) in the following proportions by weight:
  • the material according to the invention further comprises an antibacterial agent immersed in the matrix.
  • the material according to the invention further comprises at least one colorant immersed in the matrix.
  • the invention also relates to a method for manufacturing the composite material according to the invention, said method mainly comprising the following steps:
  • the second dewatering step consists of putting the impregnated substrate in a climate chamber and subjecting it to alternating cycles of holding at a temperature set between 25° C. and 28° C. and then holding at a temperature set roughly equal to ⁇ 10° C.
  • the steps of expansion and of decompression are carried out with a time delay, the impregnated and dewatered substrate being stored in packing suitable for keeping its moisture level constant.
  • the method according to the invention is completed by a final step of stabilization, during which the manufactured material is kept horizontal at room temperature until its temperature returns to room temperature naturally.
  • the third step of expansion is carried out by passing the material through a heating press for applying a counter-pressure limiting the expansion caused by the heating, and comprises the following operations:
  • the mold release agent used in the third step is parchment paper.
  • the value of the pressure applied by the press is a value previously recorded in the operating and control system of the press.
  • the value of the pressure applied by the press is between 75 and 200 tonnes.
  • the element of material produced is obtained by molding the impregnated substrate, the latter being introduced into the press in its mold, the pressure applied by the press being transmitted to the substrate by transfer of the pressure applied on its upper and lower parts of the mold.
  • the material according to the invention can advantageously be used for making elements for thermal insulation and fire protection, especially in the aeronautical field, where making savings on the on-board weight is a constant preoccupation.
  • the material according to the invention can thus advantageously be used for making:
  • FIG. 1 basic flowchart of the sequence of steps of the method for manufacturing the composite material according to the invention
  • FIG. 2 illustration of a preferred embodiment of the impregnation step of the method according to the invention
  • FIG. 3 a basic timing diagram of the alternation of the cycles of stoving employed in the context of a preferred embodiment of the dewatering step of the method according to the invention
  • FIG. 4 an illustration relating to selection of the temperature applied to the impregnated and dewatered substrate during the expansion step of the method according to the invention
  • FIGS. 5 and 6 illustrations of application of the expansion step of the method according to the invention.
  • FIGS. 7 and 8 timing diagrams illustrating the principle for the sequence of the steps of expansion of the substrate and of removal of the volatile elements trapped in the substrate, in the case of the manufacture of an element of composite material of small thickness and in the case of the manufacture of an element of composite material of greater thickness;
  • FIG. 9 basic flowchart of a variant of the sequence of steps of the method for manufacturing the composite material according to the invention, applied to the manufacture of a thick element of composite material.
  • the present invention therefore relates to a new type of composite material comprising a support, a substrate, formed from fibers of natural origin, impregnated with a mixture formed from one or more thermosetting resins and an expanding agent.
  • the fibers of natural origin are mineral or vegetable fibers in the form of felt, fibers of basalt, of flax, of hemp, of maize, of sunflower, or of bamboo in particular.
  • the natural fibers usable according to the invention can originate up to a level of 30% from recyclable materials.
  • Felt is to be understood as a nonwoven manufactured sheet, consisting of films or of layers of fibers oriented in a particular direction or at random. Said felt can be in all forms endowing it with sufficient porosity to be impregnated.
  • the use of natural fibers in the form of felt advantageously allows volume expansion of the fibers (i.e. in the three dimensions).
  • the fibers can thus be distributed uniformly through the thickness of the substrate, thus ensuring homogeneity of the final product.
  • This volume expansion contributes, moreover, to the mechanical strength as well as to the noise insulation, soundproofing and thermal performance of the composite material formed.
  • Using a felt also means that only one baking phase is required, in contrast to EP 0102335, thus limiting the energy consumption.
  • the fibers of natural origin used for manufacturing felts are generally obtained by defibering, which makes their moisture level completely random.
  • This very variable water content means that their use is specific, relative to the fibers usually employed for making composite materials, such as glass fibers.
  • the presence of water strongly impacts the reproducibility of the final product if the methods of manufacture used do not take into account the variability of the moisture content of the fibers.
  • the use of fibers of natural origin consequently requires removal of the water vapor, which is not the case with the glass or cellulose fibers usually employed in composite materials.
  • the methods described in EP 0 041 054 and EP0102335 cannot be applied as such to natural fibers.
  • the fibers of the substrate, used for making the composite material according to the invention are fibers of natural origin, among which we may notably mention basalt, flax, hemp, sunflower, bamboo or maize.
  • the fibers used are preferably basalt fibers.
  • fibers of vegetable origin whose degradation under the action of a heat flux occurs at lower temperature are not suitable as a constituent of a final material intended to be subjected to environments with high thermal stress.
  • basalt fibers of Ukrainian origin are used, or by default of Russian origin, which are characterized in particular by a relatively high level of olivine, typically above 15% (percentage by weight).
  • This level of olivine advantageously makes it possible to obtain good uniformity of the diameter of the fibers obtained by spinning and endows these fibers with advantageous performance with respect to mechanical strength and heat resistance.
  • the basalt fiber used preferably has the characteristics presented in Table 1 below.
  • the felts used are those offered by the company Basaltex and more particularly grades 4/120 and 6/130 of the range BCF Fibers Needlefelts/Mats associated with weights of 480 and 780 g/m 2 respectively.
  • the felts used are preferably needle-punched on both faces, moreover by known techniques, in order to ensure integrity of the felt during the production cycle of the expanded composite material. Needling is preferably carried out by supplying an additional polyethylene fiber.
  • the resins used for making the composite material are preferably water-based resins such as resins of the phenolic type and notably phenol-formaldehyde resins.
  • these resins offer particularly good performance for endowing the final composite material with excellent heat resistance.
  • a very endothermic phenomenon of chemical transformation produces a protective carbon-containing layer on their surface, which acts as an obstacle to transfer of this heat.
  • these resins do not produce toxic fumes, which allows them to be used for the interior equipment of cabins intended for equipping vehicles for carrying passengers.
  • the resins used can be water-based natural resins obtained from bio-sources, such as wood resins or phenolic resins of vegetable origin (grape tannins).
  • the viscosity of the resin used is suitable for the density of the felt used for making the material, so as to impregnate said felt uniformly through the thickness.
  • the use of a resin whose viscosity is unsuitable will lead to formation of a final product that is inhomogeneous or has a ratio of the percentage by weight of resin to the percentage by weight of fibers that is far from the values that endow the final product with the required mechanical, thermal and acoustic characteristics.
  • a resin with a viscosity of 300 mPa ⁇ s provides uniform impregnation of a basalt felt with a density of 780 g/m 2 .
  • the expanding agent can be selected from the expanding agents usually employed for this type of application.
  • the expanding agent preferably consists of microspheres of the Expancel® type marketed by the company Akzo Nobel.
  • the expanding agent can also be of the isobutane type or else can be selected from natural yeasts or chemical raising agents.
  • the composite material according to the invention comprises by weight between 20% and 60% of fibers of natural origin and between 40% and 80% of resin+expanded agent mixture.
  • the expanding agent is generally between 5 wt % and 25 wt % of the final composite material.
  • the composite material according to the invention comprises roughly 30 wt % of natural fibers in the form of felt and 70 wt % of a mixture consisting of resin and expanding agent.
  • the mixture of resin and expanding agent for its part roughly consists of 80% of resin and 20% of expanding agent.
  • a composite material is produced which, in comparison with the manufactured materials (wood, plastics, laminates, honeycombs, aluminum strip, etc.) commonly used in the proposed applications (cabin accommodation of aircraft, thermal boxes and partitions, inspection hatches for aircraft, etc.), advantageously has the following characteristics:
  • the composite material according to the invention does not impair the transmission of radio waves and can thus be used in applications for protection of transmitters and receivers, in radar equipment for example.
  • a material whose proportion by weight of fibers is below 20% will no longer possess adequate mechanical characteristics to envisage its application as structural material even for applications not requiring high levels of mechanical strength.
  • a material whose proportion by weight of fibers is above 40% will not have characteristics of sufficient density (after expansion), which will consequently degrade the material's capacity to resist crushing.
  • the composite material according to the invention can comprise ingredients additional to those described above, with the aim of endowing it with additional properties such as resistance to contaminating chemicals or an increase or a decrease in its electrical resistivity, or even an aesthetic character.
  • ingredients can notably be added to the aqueous mixture of resin and expanding agent, especially when they are, for example, antibacterial agents (of the lauryl-dimethyl-benzylammonium chloride type) or organometallic pigments (colorants) dispersed in the aqueous phase.
  • the composite material according to the invention can also comprise other materials and additives generally used for the applications envisaged: mold release agents, and fireproofing products notably for fibers of vegetable origin.
  • the composite material manufactured according to the invention can have a very variable density, as was mentioned above.
  • the density will be inversely proportional to the thickness of the final product. Therefore, bearing in mind that the thickness of the material manufactured according to the invention can have a thickness between 2 mm and 150 mm, the density of the material can vary in a ratio of 75 and thus can be between 20 kg/m 3 and 1500 kg/m 3 .
  • the density of the boards of material produced can also be adjusted by varying the proportion of expanding agent introduced into the mixture.
  • this proportion of expanding agent is fixed nominally at 15% (in percentage by weight of the aqueous solution) for components of large thicknesses and can be reduced to 12% for components of medium thicknesses.
  • the method of manufacture employed comprises the following steps:
  • these four manufacturing steps are preferably followed by a final step 15 of stabilization of the material produced, obtained at the end of the four manufacturing steps.
  • step 11 of impregnation of the fibers constituting the substrate 21 can be carried out by gravity by pouring the mixture of resin and expanding agent onto the substrate, as indicated by the arrows 23 , or by immersion (not shown) in a bath of the mixture of resin and expanding agent in the aqueous phase. It comprises a calendering operation.
  • the proportion by weight of resin within the felt, or degree of impregnation is in this case a function of the flow rate of the resin/expanding agent mixture, of the distance between centers of the rollers 24 and 25 of the calender as well as of the feed speed of the felt.
  • impregnation is carried out using a feed rate of the fibrous reinforcement of 2 meters per minute. Two successive impregnation passes (on both sides) can be carried out when using felt of high density in order to promote impregnation to the center of the fibrous reinforcement.
  • impregnation of the fibrous felt can also be carried out by the RTM (Resin Transfer Molding) process, which allows production of monolithic components with complex geometries and functionalized (device integration or measurement sensors for example), thus limiting the mechanical assembly operations in the proposed fields of application.
  • RTM Resin Transfer Molding
  • a substrate 22 is obtained, impregnated with resin/expanding agent mixture, which has roughly the following proportions by weight:
  • the second step 12 of dewatering of the impregnated substrate 22 consists, before the expansion step 13 , of bringing the water content of the impregnated substrate 22 to a value ideally between 10% and 13% by weight, knowing that, generally, a moisture level between 8% and 15% after dewatering is suitable for application of the next steps of the method according to the invention, the moisture level of the impregnated substrate 22 at the end of the dewatering step depending on its thickness.
  • step 12 of dewatering of the impregnated substrate can be carried out by simple evaporation with air renewal or evaporation/condensation in a confined environment so as not to destroy the structure of the fibers.
  • the impregnated substrate 22 is held for a time roughly equal to 24 hours within a climate chamber comprising an internal ventilation system, in which it is submitted, as shown in FIG. 3 , to a succession of cycles of heating 31 and of cooling 32 , the temperature to which the material is cooled or heated preferably varying between ⁇ 10° C. and +25° C.
  • the impregnated substrate thus has a controlled water content which makes it possible to carry out the next steps 13 and 14 of expansion and of removal of the water vapor. Therefore, it is then possible to proceed immediately to the next steps 13 and 14 and complete the manufacture of the material. Alternatively, it is possible to defer completion of manufacture and defer application of the third and fourth steps, proceeding to storage 111 of the impregnated and dewatered substrate. The latter must then, however, be packaged in such a way that the moisture level obtained is conserved.
  • the impregnated substrate in the form desired for the final material.
  • the impregnated substrate is dewatered while it is mounted on the template corresponding to this form, the whole being placed in the climate chamber mentioned above.
  • the third step 13 of the process for manufacturing a composite material according to the invention relates to expansion of the dewatered, impregnated substrate 22 . It is preferably carried out with heating equipment, by raising the temperature of the substrate to a temperature greater than or equal to the temperature of expansion of the expanding agent, for example to a temperature generally between 75° C. and 180° C., preferably between 90° and 130° C. As an alternative, it can be carried out by exposing the impregnated and dewatered substrate to low or hyper-frequency electromagnetic radiation.
  • this step is carried out by means of a heating press, the temperature of heating preferably being between 130° C. and 180° C., a temperature that permits both activation of the expanding agent and crosslinking of the resin.
  • the heating press advantageously allows application of a counter-pressure limiting the expansion of the material caused by the heating.
  • the time in the press is moreover defined, as illustrated by the nomogram in FIG. 4 , as a function of the thickness (and therefore of the density) of the material to be produced for the application considered.
  • the use of a heating press advantageously makes it possible to control the final thickness, after expansion, of the material 18 produced.
  • step 13 of expansion of the composite material according to the invention comprises carrying out the following operations:
  • the counter-pressure imposed on the impregnated substrate to limit its expansion to the desired value will thus typically be between 75 and 200 tonnes, for the applications envisaged.
  • the fourth step 14 of the process for manufacturing a composite material 18 according to the invention relates to proceeding to said removal.
  • This step the duration of which is notably a function of the thickness of the element of material produced, or of the component produced, is indispensable for maintaining the integrity of said component.
  • the element of composite material produced has a complex geometry, with faces that are not flat, curved faces for example, the production of such an element requiring placing, between the platens of the press, a mold that completely imprisons the element.
  • a flat element of standard thickness ⁇ 12 mm
  • the water vapor trapped in the material escapes naturally at the edge of the element, the blocks being prepositioned in order to calibrate the thickness, providing vents sufficient for removal of the volatile elements during the expansion phase.
  • this step of removal 14 of the water vapor mainly follows the expansion phase 13 . It consists of producing a partial decompression which allows the water vapor, initially present within the impregnated substrate, to escape.
  • step suitable for manufacturing components of material with a thickness less than or equal to 12 mm, said step, lasting approximately 30 seconds, is carried out just once, after step 13 , as shown in FIG. 7 and FIG. 1 .
  • removal of the water from the impregnated substrate may require carrying out the single step 14 several times, twice for example. In this case, it is carried out a first time 141 before execution of the expansion phase 13 and a second time 142 afterwards, as shown in FIG. 8 and FIG. 9 .
  • a final step 15 of stabilization consisting of leaving the manufactured element of material 18 at rest in a horizontal plane for a sufficient time to return to room temperature naturally.
  • resting of the element of material lasts at least 2 hours.
  • This final step of stabilization notably allows relaxation of the mechanical stresses within the material, and this relaxation guarantees its integrity (i.e. absence of internal defects) as well as maintaining its dimensional characteristics.
  • An element of composite material 19 is then obtained that is ready to be used for producing the desired object or structure.
  • the material according to the invention thus produced can, depending on the use for which it is intended, undergo additional operations such as painting, deposition of a surface coating forming a mechanical reinforcement or endowing the material with certain aesthetic characteristics.
  • a composite material is obtained that has characteristics of composition and of structure, as well as physical characteristics (mechanical, thermal and acoustic) of a nature to constitute a solution to the problems mentioned above, problems for which the existing composite materials do not provide a satisfactory solution.
  • This example relates to the production of a composite material with basalt fibers for aeronautical application.
  • This material is designated ROXALTE® by the applicant.
  • the material is a composite material according to the invention, produced following the steps of the method according to the invention, recalled below:
  • the material in question is obtained starting from a mixture 17 of resin, expanding agent and water, the whole being mixed mechanically within a vertical mixer of the Lödige type, or on a device of the drum inverting type, for about 20 minutes.
  • the phenolic resin/expanding agent mixture is in this case prepared in such a way that the proportions of the final mixture are as presented in Table 2 below.
  • the mixture described above is mixed mechanically in a vertical mixer of the Lödige type for 10 minutes (time for attaining homogeneity of the mixture).
  • the above mixture is used for carrying out impregnation 11 by gravity and calendering of a felt 16 whose weight is 780 g/m 2 , said felt being distributed commercially by the company Basaltex under reference 6/130 from the range BCF Fibers Needlefelts/Mats, the required reinforcement/resin final weight ratio, adjusted by calendering, being 30/70.
  • the felt 11 After impregnation with the phenolic resin, the felt 11 undergoes a step 12 of dewatering for 24 hours, which follows the thermal cycle presented in FIG. 3 .
  • the expansion step 13 is in this case carried out by means of a press with a machine pressure of 80 tonnes.
  • test plates 10 ⁇ 10 inches
  • Thicknesses tested 7 and 14 mm
  • Density of the material 150 and 300 kg/m 3

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Publication number Priority date Publication date Assignee Title
US10882048B2 (en) 2016-07-11 2021-01-05 Resource Fiber LLC Apparatus and method for conditioning bamboo or vegetable cane fiber
WO2019199538A1 (en) * 2017-04-12 2019-10-17 Resource Fiber LLC Bamboo and/or vegetable cane fiber ballistic impact panel and process
US11175116B2 (en) 2017-04-12 2021-11-16 Resource Fiber LLC Bamboo and/or vegetable cane fiber ballistic impact panel and process
US10597863B2 (en) 2018-01-19 2020-03-24 Resource Fiber LLC Laminated bamboo platform and concrete composite slab system

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BR112013020606A2 (pt) 2016-10-18
UA109050C2 (en) 2015-07-10
FR2956664A1 (fr) 2011-08-26
IL227744A0 (en) 2013-09-30
US20140220841A1 (en) 2014-08-07
IL227744A (en) 2016-05-31
CN103797052A (zh) 2014-05-14

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